Abstract
This work focuses on the electrochemical reduction behavior of PO43– ions in molten CaCl2 at 1123 K, aiming to develop a next-generation process for producing white phosphorus (P4) through electrolysis of dissolved PO43–. Results from cyclic voltammetry indicate a shift for the electrochemical reduction of PO43– from a reversible reaction to a quasi-reversible one as the potential scan rate increases. The detachment rate of P4 gas was found to be higher at the graphite electrode compared to Mo and W electrodes. The apparent diffusion coefficient of PO43–, determined from chronoamperometry and chronopotentiometry at a graphite electrode, ranges from 1.43 to 2.26 × 10–4 cm2 s–1. Additionally, an increase in the concentration of O2– was found to decrease the detachment rate of P4 gas, likely due to changes in the melt's physical properties. However, the increase in O2– up to 0.30 mol% does not significantly affect the diffusion of PO43–. This study provides valuable insights into the electrochemistry of PO43– in molten CaCl2 and offers a theoretical guidance for the technology development of P4 production through electrolysis.
Published Version
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